EP3478777B1 - Composition formant un film diélecttrique - Google Patents

Composition formant un film diélecttrique Download PDF

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Publication number
EP3478777B1
EP3478777B1 EP18773066.8A EP18773066A EP3478777B1 EP 3478777 B1 EP3478777 B1 EP 3478777B1 EP 18773066 A EP18773066 A EP 18773066A EP 3478777 B1 EP3478777 B1 EP 3478777B1
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Prior art keywords
meth
dielectric film
acrylate
weight
optionally
Prior art date
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EP18773066.8A
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German (de)
English (en)
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EP3478777A1 (fr
EP3478777A4 (fr
Inventor
Sanjay Malik
William A. Reinerth
Ognian Dimov
Raj Sakamuri
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Fujifilm Electronic Materials USA Inc
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Fujifilm Electronic Materials USA Inc
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • H01L23/5329—Insulating materials

Definitions

  • US 2009/0288764 A1 describes a process for manufacturing a thin freestanding film made from amorphous polymers including polyimide.
  • US 2002/0131247 A1 describes a dielectric resin composition including a polyimide resin with side chain epoxy groups.
  • Dielectric material requirements for packaging applications are continuously evolving as these new, advanced devices are relying heavily on wafer and panel-level packaging (WLP and PLP) and 3D integration.
  • High density interconnect (HDI) architectures consisting of multiple dielectric buildup layers connected through a multistage via structure are being utilized to pack more computing power into smaller spaces.
  • HDI high density interconnect
  • Excimer laser ablation of dielectric films is one of the convenient techniques to achieve this level of patterning.
  • a large amount of debris is formed during the ablation process. Presence of debris can interfere with copper deposition process by preventing uniform seed layer deposition.
  • this disclosure features a novel dielectric film (e.g., a self-standing film) formed by the composition described herein.
  • the dielectric film can contain: a) at least one fully imidized polyimide polymer; b) at least one metal-containing (meth)acrylates (e.g., an uncrosslinked metal-containing (meth)acrylate); and c) at least one catalyst.
  • the dielectric film can includes (e.g., after crosslinking): a) at least one fully imidized polyimide polymer; and b) at least one crosslinked metal-containing (meth)acrylates.
  • this disclosure features a process to deposit a conductive metal layer (e.g., creating an embedded copper trace structure) that includes step of:
  • this disclosure features a method for preparing a dry film structure.
  • the method includes:
  • the term “fully imidized” means the polyimide polymers of this disclosure are at least about 90% (e.g., at least about 95%, at least about 98%, at least about 99%, or about 100%) imidized.
  • metal-containing (meth)acrylates MCA refer to compounds containing a metal and (meth)acrylate ligands.
  • the (meth)acrylate ligands of MCA are sufficiently reactive to enable the MCA to participate in free radical-induced crosslinking of the MCA-containing film.
  • the term “(meth)acrylates” include both acrylates and methacrylates.
  • the catalyst e.g., an initiator
  • a crosslinker is a compound containing two or more alkenyl or alkynyl groups capable of a crosslinking or polymerization reaction in the presence of a catalyst.
  • this disclosure features a dielectric film forming composition containing:
  • the at least one fully imidized polyimide polymer of the dielectric film forming composition is prepared by reaction of at least one diamine with at least one dicarboxylic acid dianhydride.
  • suitable diamines include, but are not limited to, 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (alternative names including 4,4'-[1,4-phenylene-bis(1-methylethylidene)] bisaniline), 1-(4-aminophenyl)-1,3,3-trimethyl-2H-inden-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-indan-5-amine, [1-(4-aminophenyl)-1,3,3-trimethyl-indan-5-yl]amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 5-amino-6-methyl-1-(3'-amin
  • tetracarboxylic acid dianhydride monomers include, but are not limited to, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindan-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindan-6,7-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindan-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindan-6,7-dicarboxylic acid anhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, norbornane-2,3,5,6-tetracar
  • More preferred tetracarboxylic acid dianhydride monomers include 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride. Any of these tetracarboxylic acid dianhydride can be used individually or in combination in any ratio as long as the resulting polyimide polymer satisfies the requirements of this disclosure.
  • the polyimide polymer thus formed can be soluble in an organic solvent.
  • the polyimide polymer can have a solubility in an organic solvent of at least about 50 mg/mL (e.g., at least about 100 mg/mL or at least about 200 mg/mL) at 25°C.
  • organic solvents include, but are not limited to, lactones such as gamma-butyrolactone, ⁇ -caprolactone, ⁇ -caprolactone and ⁇ -valerolactone, cycloketones such as cyclopentanone and cyclohexanone, linear ketones such as methyl ethyl ketone (MEK), esters such as n-butyl acetate, ester alcohol such as ethyl lactate, ether alcohols such as tetrahydrofurfuryl alcohol, glycol esters such as propylene glycol methyl ether acetate, and pyrrolidones such as n-methyl pyrrolidone.
  • lactones such as gamma-butyrolactone, ⁇ -caprolactone, ⁇ -caprolactone and ⁇ -valerolactone
  • cycloketones such as cyclopentanone and cyclohexanone
  • linear ketones such as methyl
  • a polyimide precursor polymer is prepared first.
  • the PI precursor polymer is a polyamic acid (PAA) polymer.
  • the PI precursor is a polyamic ester (PAE) polymer.
  • one or more diamine(s) are combined with one or more tetracarboxylic acid dianhydride(s) in at least one (e.g., two, three, or more) polymerization solvent to form a polyamic acid (PAA) polymer.
  • the PAA polymer formed is imidized, either chemically or thermally, to form a PI polymer.
  • the PAA polymer is end-capped by using an appropriate reagent during or after the polymer synthesis.
  • the PAA polymer formed is esterified to form a polyamic ester (PAE) polymer.
  • PAE polyamic ester
  • the PAE polymer is formed by combination of a tetracarboxylic half ester with one or more diamines in at least one polymerization solvent.
  • the PAE polymer is end-capped by using an appropriate agent.
  • an end-capped PI polymer is synthesized from a PAA polymer or a PAE polymer containing an end-cap group. In some embodiments, such a PI polymer is end-capped after imidization.
  • a chemical imidizing agent e.g., a dehydrating agent
  • a PAA polymer e.g., a PAA polymer
  • suitable dehydrating agents include, but are not limited to, trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, ethanesulfonic acid, butanesulfonic acid, perfluorobutanesulfonic acid, acetic anhydride, propionic anhydride, and butyric anhydride.
  • this dehydration process can be catalyzed by further addition of a basic catalyst.
  • suitable basic catalysts include, but are not limited to, pyridine, triethylamine, tripropylamine, tributylamine, dicyclohexylmethylamine, 2,6-lutidine, 3,5-lutidine, picoline, 4-dimethylaminopyridine (DMAP) and the like.
  • the polymerization solvent(s) for preparing PI polymers or their precursors is generally one or a combination of two or more polar, aprotic solvents.
  • Suitable polar, aprotic solvents include, but are not limited to, dimethylformamide (DMF), dimethylacetamide (DMAc), N-formylmorpholine (NFM), N-methylpyrrolidinone (NMP), N-ethylpyrrolidinone (NEP), dimethylsulfoxide (DMSO), gamma-butyrolactone (GBL), hexamethyl phosphoric acid triamide (HMPT), tetrahydrofuran (THF), methyltetrahydrofuran, 1,4-dioxane and mixtures thereof.
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • NFM N-formylmorpholine
  • NMP N-methylpyrrolidinone
  • NEP N-ethylpyrrolidinone
  • the weight average molecular weight (Mw) of the polyimide polymer described herein is at least about 5,000 Daltons (e.g., at least about 10,000 Daltons, at least about 20,000 Daltons, at least about 25,000 Daltons, at least about 30,000 Daltons, at least about 35,000 Daltons, at least about 40,000 Daltons, or at least about 45,000 Daltons) and/or at most about 100,000 Daltons (e.g., at most about 90,000 Daltons, at most about 80,000 Daltons at most about 70,000 Daltons, at most about 65,000 Daltons, at most about 60,000 Daltons, at most about 55,000 Daltons, or at most about 50,000 Daltons).
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the polyimide polymer is from about 20,000 Daltons to about 70,000 Daltons or from about 30,000 Daltons to about 80,000 Daltons.
  • the weight average molecular weight can be obtained by gel permeation chromatography methods and calculated using a polystyrene standard.
  • the amount of polyimide (A) is at least about at least about 3 weight % (e.g., at least about 6 weight %, at least about 9 weight %, at least about 12 weight %, or at least about 15 weight %) and/or at most about 40 weight % (e.g., at most about 35 weight %, at most about 30 weight %, at most about 25 weight %, or at most about 20 weight %) of the entire weight of the dielectric film forming composition (including any solvent).
  • the amount of polyimide (A) is at least about 10 weight % (e.g., at least about 12.5 weight %, at least about 15 weight %, at least about 20 weight %, or at least about 25 weight %) and/or at most about 60 weight % (e.g., at most about 55 weight %, at most about 50 weight %, at most about 45 weight %, at most about 40 weight %, at most about 35 weight %, or at most about 30 weight %) of the amount of solid in the dielectric film forming composition.
  • the amount of solid in the dielectric film forming composition refers to the entire weight of the composition minus the amount of solvent in the composition, or the entire weight of the dielectric film formed by the composition.
  • Metal-containing (meth)acrylates (MCAs) useful in the present disclosure generally have sufficient compatibility with other ingredients in the dielectric film forming composition and are readily dispersed or dissolved in the composition upon mixing.
  • the MCAs may be incorporated into the dielectric film forming composition as a solid or as a solution.
  • the MCA-containing compositions do not form phase separation (becomes visibly heterogeneous) upon standing over the course of at least 24 hours at 25 °C.
  • dielectric films formed from the MCA-containing compositions generally are visibly clear and homogenous.
  • Suitable metal atoms useful for the MCAs in the present disclosure include titanium, zirconium, hafnium, and germanium.
  • the MCAs include at least one metal atom and at least one (e.g., one, two, three, or four) (meth)acrylate group.
  • Preferred MCAs contain three or four (meth)acrylate groups attached to each metal atom.
  • suitable MCAs include, but are not limited to, titanium tetra(meth)acrylate, zirconium tetra(meth)acrylate, hafnium tetra(meth)acrylate, titanium butoxide tri(meth)acrylate, titanium dibutoxide di(meth)acrylate, titanium tributoxide(meth)acrylate, zirconium butoxide tri(meth)acrylate, zirconium dibutoxide di(meth)acrylate, zirconium tributoxide (meth)acrylate, hafnium butoxide tri(meth)acrylate, hafnium dibutoxide di(meth)acrylate, hafnium tributoxide(meth)acrylate, titanium tetra(carboxyethyl(meth)acrylate), zirconium tetra(carboxyethyl(meth)acrylate), hafnium tetra(carboxyethyl (meth)acrylate), titanium
  • the (meth)acrylate groups of the MCAs are sufficiently reactive to enable the MCAs to participate in crosslinking or polymerization of the MCA-containing film induced by free radicals, which may be generated by one or more catalysts present in the dielectric film forming composition.
  • the crosslinking or polymerization can occur among at least two MCAs or among at least one MCA and at least one non-MCA crosslinker in the dielectric film forming composition.
  • an MCA is a crosslinker (e.g., when the MCA includes two or more (meth)acrylate groups).
  • an MCA is a monomer suitable for polymerization or function as a chain terminator (e.g., when the MCA includes only one (meth)acrylate group).
  • the MCA is not crosslinked (e.g., when the MCA includes only one (meth)acrylate group) in a crosslinked dielectric film formed by the compositions described herein.
  • the amount of the at least one MCA is at least about 0.5 weight % (e.g., at least about 1 weight %, at least about 2 weight %, at least about 3 weight %, at least about 4 weight %, or at least about 5 weight %) and/or at most about 20 weight % (e.g., at most about 18 weight %, at most about 16 weight %, at most about 14 weight %, at most about 12 weight %, or at most about 10 weight %) of the entire weight of the dielectric film forming composition.
  • the amount of the MCA is at least about 1 weight % (e.g., at least about 2 weight %, at least about 4 weight %, at least about 6 weight %, at least about 8 weight %, or at least about 10 weight %) and/or at most about 25 weight % (e.g., at most about 20 weight %, at most about 18 weight %, at most about 16 weight %, at most about 14 weight %, or at most about 12 weight %) of the amount of solid in the dielectric film forming composition.
  • the presence of at least one MCA in the dielectric film forming composition can minimize generation of debris when the dielectric film formed by the composition is patterned by using a laser ablation process.
  • the dielectric film forming composition of this disclosure can include at least one catalyst (e.g., an initiator).
  • the catalyst is capable of inducing crosslinking or polymerization reaction when exposed to heat and/or source of radiation.
  • the catalyst used is a photoinitiator, where the photoinitiator is a compound capable of generating free radicals when exposed to high energy radiation.
  • high energy radiation include electron beams, ultraviolet light, and X-ray.
  • the photoinitiator induces a crosslinking or polymerization reaction involving the (meth)acrylate groups of the MCA compound and/or other entities present in the composition that are capable of undergoing crosslinking or polymerization reaction.
  • examples of such entities include crosslinkers (e.g., non-MCA crosslinkers) and polyimides bearing alkenyl and alkynyl functional groups.
  • photoinitiators include, but are not limited to, 1,8-octanedione, 1,8-bis[9-(2-ethylhexyl)-6-nitro-9H-carbazol-3-yl]-1,8-bis(O-acetyloxime), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 from BASF), a blend of 1-hydroxycyclohexylphenylketone and benzophenone (Irgacure 500 from BASF), 2,4,4-trimethylpentyl phosphine oxide (Irgacure 1800, 1850, and 1700 from BASF), 2,2-dimethoxyl-2-acetophenone (Irgacure 651from BASF), bis(2,4,6-trimethyl benzoyl)phenyl phosphine oxide (Irgacure 819 from BASF), 2-methyl-1-[4-[4
  • nonionic-type photoinitiators include (5-toluylsulfonyloxyimino-5H-thiophen-2-ylidene)-2-methylphenyl-acetonitrile (Irgacure 121 from BASF), phenacyl p-methylbenzenesulfonate, benzoin p-toluenesulfonate, (p-toluene-sulfonyloxy)methylbenzoin, 3-(p-toluenesulfonyloxy)-2-hydroxy-2-phenyl-1-phenylpropyl ether, N-(p-dodecylbenzenesulfonyloxy)-1,8-naphthalimide, N-(phenyl-sulfonyloxy)-1,8-napthalimide, bis(cyclohexylsulfonyl)diazomethane, 1-p-toluenesulfonyl-1
  • a photosensitizer can be used in the dielectric film forming composition where the photosensitizer can absorb light in the wavelength range of 193 to 405 nm.
  • photosensitizers include, but are not limited to, 9-methylanthracene, anthracenemethanol, acenaphthylene, thioxanthone, methyl-2-naphthyl ketone, 4-acetylbiphenyl, and 1,2-benzofluorene.
  • the catalyst used is a thermal initiator where the thermal initiator is a compound capable of generating free radicals when exposed to a temperature from about 70°C to about 250°C.
  • the thermal initiator induces a crosslinking or polymerization reaction involving (meth)acrylate groups of the MCA compound and/or other entities present in the composition that are capable of undergoing crosslinking or polymerization reaction.
  • entities include crosslinkers (e.g., non-MCA crosslinkers) and polyimides bearing alkenyl and alkynyl functional groups.
  • thermal initiators include, but are not limited to, benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tert-amyl peroxybenzoate, tert-butyl hydroperoxide, dicumyl peroxide, cumene hydroperoxide, succinic acid peroxide, di(n-propyl)peroxydicarbonate, 2,2-azobis(isobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobisisobutyrate, 4,4-azobis(4-cyanopentanoic acid), azobiscyclohexanecarbonitrile, 2,2-azobis(2-methylbutyronitrile) and the like.
  • a combination of two or more catalysts can be used in the dielectric film forming composition.
  • the combination of catalysts can be all thermal initiators, all photoinitiators, or a combination of thermal initiators and photoinitiators.
  • the amount of catalyst is at least about 0.25 weight % (e.g., at least about 0.5 weight %, at least about 0.75 weight %, at least about 1.0 weight %, or at least about 1.5 weight %) and/or at most about 4.0 weight % (e.g., at most about 3.5 weight %, at most about 3.0 weight %, at most about 2.5 weight %, or at most about 2.0 weight%) of the entire weight of the dielectric film forming composition.
  • the amount of catalyst is at least about 0.5 weight % (e.g., at least about 1.0 weight %, at least about 1.5 weight %, at least about 2.0 weight %, or at least about 2.5 weight %) and/or at most about 5.0 weight % (e.g., at most about 4.5 weight %, at most about 4.0 weight %, at most about 3.5 weight %, or at most about 3.0 weight%) of the amount of solid in the dielectric film forming composition.
  • 0.5 weight % e.g., at least about 1.0 weight %, at least about 1.5 weight %, at least about 2.0 weight %, or at least about 2.5 weight
  • 5.0 weight % e.g., at most about 4.5 weight %, at most about 4.0 weight %, at most about 3.5 weight %, or at most about 3.0 weight
  • the organic solvent can be gamma -butyrolactone (GBL), cyclopentanone (CP), cyclohexanone, n-butyl alcohol, N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), or a mixture thereof.
  • GBL gamma -butyrolactone
  • CP cyclopentanone
  • NMP N-methyl-2-pyrrolidone
  • DMSO dimethylsulfoxide
  • the amount of the organic solvent in the dielectric film forming composition is at least about 35 weight % (e.g., at least about 40 weight %, at least about 45 weight %, at least about 50 weight %, at least about 55 weight %, at least about 60 weight %, or at least about 65 weight %) and/or at most about 98 weight % (e.g., at most about 95 weight %, at most about 90 weight %, at most about 85 weight %, at most about 80 weight%, at most about 75 weight% or at most about 70 weight%) of the entire weight of the dielectric film forming composition.
  • the dielectric film forming composition of this disclosure can further include at least one crosslinker (e.g., a non-MCA crosslinker).
  • the crosslinker contains two or more alkenyl or alkynyl groups.
  • the crosslinker can be capable of undergoing a crosslinking or polymerization reaction in the presence of a catalyst.
  • the at least one crosslinker is at least one urethane acrylate oligomer.
  • urethane acrylate oligomer refers to a class of urethane (meth)acrylate compounds that contain urethane linkages and have (meth)acrylate (e.g., acrylate or methacrylate) functional groups such as urethane multi(meth)acrylate, multiurethane (meth)acrylate, and multiurethane multi(meth)acrylate.
  • Types of urethane (meth)acrylate oligomers have been described by, for example, Coady et al., U.S.
  • urethane acrylate oligomers useful in the present disclosure include, but are not limited to, CN9165US, CN9167US, CN972, CN9782, CN9783 and CN992. These and other urethane acrylate oligomers are commercially available from Arkema (Sartomer).
  • the crosslinker contains at least two (meth)acrylate groups.
  • the crosslinker is selected from the group consisting of 1,6-hexanediol di(meth)acrylate, tetraethyleneglycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propoxylated (3) glycerol tri(meth)acrylate, divinylbenzene, ethoxylated bisphenol-A-di(meth)acrylate, diethylene glycol bis(allyl carbonate), trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol
  • the amount of the crosslinker in the dielectric film forming composition is at least about 2.5 weight % (e.g., at least about 5 weight %, at least about 7.5 weight %, at least about 10 weight %, at least about 12.5 weight %, or at least about 15 weight %) and/or at most about 30 weight % (e.g., at most about 27.5 weight %, at most about 25 weight %, at most about 22.5 weight %, at most about 20 weight%, or at most about 17.5 weight%) of the entire weight the composition.
  • the amount of the crosslinker in the dielectric film-forming composition is about 5 weight % (e.g., at least about 10 weight %, at least about 15 weight %, at least about 20 weight %, at least about 25 weight %, or at least about 30 weight %) and/or at most about 60 weight % (e.g., at most about 55 weight %, at most about 50 weight %, at most about 45 weight %, at most about 40 weight%, or at most about 35 weight%) of the amount of solid in the composition.
  • the crosslinker can improve the mechanical properties and chemical resistance of the dielectric film formed by the compositions described herein.
  • the dielectric film forming composition of this disclosure can optionally include other components such as adhesion promoters, fillers, surfactants, plasticizers, copper passivation reagents, colorants, and dyes.
  • the dielectric film forming composition of this disclosure further includes one or more adhesion promoter.
  • adhesion promoters are described in " Silane Coupling Agent" Edwin P. Plueddemann, 1982 Plenum Press, New York .
  • Classes of adhesion promoters include, but are not limited to, mercaptoalkoxysilanes, aminoalkoxysilanes, epoxyalkoxysilanes, glycidyloxyalkoxysilanes, mercaptosilanes, cyanatosilanes and imidazole silanes.
  • the adhesion promoter contains both an alkoxsilyl group and a functional group containing carbon-carbon multiple bond selected from substituted or unsubstituted alkenyl groups and substituted or unsubstituted alkynyl groups.
  • the amount of the optional adhesion promoter in the dielectric film forming composition is at least about 0.3 weight % (e.g., at least about 0.5 weight %, at least about 0.7 weight %, or at least about 1 weight %) and/or at most about 4 weight % (e.g., at most about 3 weight %, at most about 2 weight %, or at most about 1.5 weight%) of the entire weight of the composition.
  • the amount of the optional adhesion promoter in the dielectric film forming composition is at least about 0.5 weight % (e.g., at least about 1 weight %, at least about 2 weight %, or at least about 2.5 weight %) and/or at most about 8 weight % (e.g., at most about 6 weight %, at most about 5 weight %, at most about 4 weight %, or at most about 3 weight%) of the amount of solid in the composition.
  • the dielectric film forming composition of this disclosure can further include one or more filler.
  • the filler is an inorganic particle.
  • the inorganic particle is selected from the group consisting of silica, alumina, titania, zirconia, hafnium oxide, CdSe, CdS, CdTe, CuO, zinc oxide, lanthanum oxide, niobium oxide, tungsten oxide, strontium oxide, calcium titanium oxide, sodium titanate, barium sulfate, barium titanate, barium zirconate, and potassium niobate.
  • the inorganic fillers are in a granular form of an average size of about 0.1-20 microns.
  • the filler is an organic particle where the organic particle is insoluble in the solvent of the composition.
  • organic particles include, but are not limited to, cross-linked rubber particles, cross-linked or non-crosslinked polyimide particles, and cross-linked polymer particles.
  • Silica fillers useful in the present disclosure may be hydrophilic or hydrophobic. Hydrophobic silica fillers can be produced by surface modification of hydrophilic, fumed silica or by direct formation of surface modified silica fillers. Direct formation of surface modified silica fillers is typically accomplished by hydrolytic condensation of functional silanes. Surface modified silica fillers useful in the present disclosure may have reactive and/or non-reactive groups on their surface. Fillers (e.g., silica fillers) useful in the present disclosure have particle sizes (e.g., mean particle sizes) of at most about 2 microns (e.g.
  • the filler size distribution can be narrow (e.g., essentially monodisperse) or broad.
  • the desired filler size and distribution can be achieved by any of a number of techniques known to those skilled in the art including, but not limited to, milling, grinding and filtration.
  • the silica fillers are dispersed in an organic solvent.
  • Dispersion in a solvent can be accomplished by a variety of methods known to those skilled in the art including, but not limited to, media milling and high shear mixing.
  • Solvents useful for dispersion of silica fillers are not particularly limited.
  • Preferred solvents include esters, ethers, lactones, ketones, amides, and alcohols. More preferred solvents include GBL, cyclopentanone, cyclohexanone, ethyl lactate, and n-butanol.
  • the amount of the filler (e.g., silica filler) in the dielectric film forming composition of this disclosure is at least about 2 weight % (e.g., at least about 4 weight %, at least about 6 weight %, at least about 8 weight %, or at least about 10 weight %) and/or at most about 20 weight % (e.g., at most about 18 weight %, at most about 15 weight %, or at most about 12 weight %) of the entire weight of the composition.
  • the amount of the filler (e.g., silica filler) in the dielectric film forming composition of this disclosure is at least about 5 weight % (e.g., at least about 10 weight %, at least about 14 weight %, at least about 17 weight %, or at least about 20 weight %) and/or at most about 40 weight % (e.g., at most about 35 weight %, at most about 30 weight %, or at most about 25 weight %) of the amount of solid in the composition.
  • the dielectric film forming composition of this disclosure can also optionally contain one or more surfactant. If a surfactant is employed, the amount of the surfactant is at least about 0.001 weight % (e.g., at least about 0.01 weight % or at least about 0.1 weight %) and/or at most about 2 weight % (e.g., at most about 1 weight % or at most about 0.5 weight %) of the entire weight of the dielectric film forming composition.
  • a surfactant is employed, the amount of the surfactant is at least about 0.001 weight % (e.g., at least about 0.01 weight % or at least about 0.1 weight %) and/or at most about 2 weight % (e.g., at most about 1 weight % or at most about 0.5 weight %) of the entire weight of the dielectric film forming composition.
  • the amount of the surfactant is at least about 0.002 weight % (e.g., at least about 0.02 weight % or at least about 0.2 weight %) and/or at most about 4 weight % (e.g., at most about 1 weight % or at most about 0.5 weight %) of the amount of solid in the composition.
  • surfactants include, but are not limited to, the surfactants described in JP-A-62-36663 , JP-A-61-226746 , JP-A-61-226745 , JP-A-62-170950 , JP-A-63-34540 , JP-A-7-230165 , JP-A-8-62834 , JP-A-9-54432 and JP-A-9-5988 .
  • the dielectric film forming composition of the present disclosure can optionally contain one or more plasticizers.
  • the amount of the optional plasticizer, if employed, is at least about 1 weight % (e.g., at least about 2 weight % or at least about 3 weight %) and/or at most about 10 weight % (e.g., at most about 7.5 weight % or at most about 5 weight %) of the entire weight of the dielectric film forming composition.
  • the amount of the optional plasticizer is at least about 2 weight % (e.g., at least about 4 weight % or at least about 6 weight %) and/or at most about 20 weight % (e.g., at most about 14 weight % or at most about 10 weight %) of the amount of solid in the composition.
  • the dielectric film forming composition of the present disclosure can optionally contain one or more copper passivation reagent.
  • copper passivation reagents include triazole compounds, imidazole compounds and tetrazole compounds.
  • Triazole compounds can include triazoles, benzotriazoles, substituted triazoles, and substituted benzotriazoles.
  • substituents include C 1 -C 8 alkyl, amino, thiol, mercapto, imino, carboxy and nitro groups.
  • imidazole compounds include, but are not limited to, 2-alkyl-4-methyl imidazole, 2-phenyl-4-alkyl imidazole, 2-methyl-4(5)-nitroimidazole, 5-methyl-4-nitroimidazole, 4-imidazolemethanol hydrochloride, 2-mercapto-1-methylimidazole.
  • tetrazole compounds include, but are not limited to, 1-H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole,1-phenyl-5-mercapto-1H-tetrazole, 5,5'-bis-1H-tetrazole,1-methyl-5-ethyltetrazole, 1-methyl-5-mercaptotetrazole, 1-carboxymethyl-5-mercaptotetrazole, and the like.
  • the amount of the optional copper passivation agent, if employed, is at least about 0.01 weight % (e.g. at least about 0.05 weight % at least about 0.1 weight % or at least about 0.5 weight %) and/or at most about 2 weight % (e.g., at most about 1.5 weight % or at most about 1 weight %) of the entire weight of the dielectric film forming composition.
  • the amount of the optional copper passivation agent is at least about 0.02 weight % (e.g., at least about 0.1 weight %, at least about 0.2 weight % or at least about 1 weight %) and/or at most about 4 weight % (e.g., at most about 3 weight % or at most about 2 weight %) of the amount of solid in the composition.
  • the dielectric film forming composition of the present disclosure can optionally contain one or more dyes and/or one or more colorants.
  • the polyimide can be prepared from diamines excluding the siloxane diamine of Structure (1) in which R 1 and R 2 are each independently a divalent aliphatic or aromatic group (e.g., a C1-6 divalent aliphatic group or a C 6-12 divalent aromatic group), R 3 , R 4 , R 5 and R 6 are each independently a monovalent aliphatic or aromatic group (e.g., a C 1-6 monovalent aliphatic group or a C 6-12 monovalent aromatic group), and m is an integer of 1 - 100.
  • R 1 and R 2 are each independently a divalent aliphatic or aromatic group (e.g., a C1-6 divalent aliphatic group or a C 6-12 divalent aromatic group)
  • R 3 , R 4 , R 5 and R 6 are each independently a monovalent aliphatic or aromatic group (e.g., a C 1-6 monovalent aliphatic group or a C 6-12 monovalent aromatic group)
  • m is an integer
  • Examples of monomer of siloxane diamines of structure (III) include, but are not limited to:
  • the dielectric film forming compositions of the present disclosure may specifically exclude one or more of the following solvents, in any combination, if more than one.
  • solvents can be selected from the group consisting of linear ketones such as methyl ethyl ketone (MEK), esters such as ethyl acetate, ester alcohols such as ethyl lactate, ether alcohols such as tetrahydrofurfuryl alcohol, and glycol esters such as propylene glycol methyl ether acetate (PGMEA).
  • MEK methyl ethyl ketone
  • esters such as ethyl acetate
  • ester alcohols such as ethyl lactate
  • ether alcohols such as tetrahydrofurfuryl alcohol
  • glycol esters such as propylene glycol methyl ether acetate (PGMEA).
  • the dielectric film forming compositions of the present disclosure may specifically exclude one or more of the following adhesion promoters, in any combination, if more than one.
  • adhesion promoters can be selected from the group consisting of primary amine containing adhesion promoters (such as 3-aminopropyl triethoxysilane and m-aminophenyl triethoxysilane), secondary amine containing adhesion promoters (such as N-cyclohexylamino trimethoxysilane), tertiary amine containing adhesion promoters (such as diethylaminoethyl triethoxysilane), urea containing adhesion promoters (such as ureidopropyl trimethoxysilane), anhydride containing adhesion promoters (such as 3-(triethoxysilyl)propyl succinic anhydride), epoxy containing adhesion promoters (such as 2-(3,4-e
  • the dielectric film forming compositions of the present disclosure may specifically exclude one or more of additive components, in any combination, if more than one.
  • additive components can be selected from the group consisting of non-polyimide polymers, non-crosslinking non-polyimide polymers, surfactants, plasticizers, , colorants, dyes, water, oxygen scavengers, quaternary ammonium hydroxides, amines, alkali metal and alkaline earth bases (such as NaOH, KOH, LiOH, magnesium hydroxide, and calcium hydroxide), fluoride containing monomeric compounds, oxidizing agents (e.g., peroxides, hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, tetramethyl
  • the dielectric film forming composition of the present disclosure can minimize generation of debris when the dielectric film formed by the composition is patterned by using a laser ablation process.
  • a conductive metal layer e.g., a copper layer
  • the process does not require a debris removal process or a pretreatment process before coating a seed layer (e.g., including a barrier layer and a metal seeding layer.
  • this disclosure features a dielectric film formed by the dielectric film forming composition described herein.
  • the dielectric film when the dielectric film is not yet crosslinked by exposing to a source of radiation or heat, can include: a) at least one fully imidized polyimide polymer; b) at least one metal-containing (meth)acrylates; and c) at least one catalyst.
  • the dielectric film can further include at least one crosslinker (such as those described above with respect to the dielectric film forming composition).
  • the dielectric film when the dielectric film has been crosslinked by exposing to a source of radiation or heat, can include a) at least one fully imidized polyimide polymer; b) at least one crosslinked metal-containing (meth)acrylate; and c) optionally at least one inorganic filler.
  • the at least one fully imidized polyimide polymer can be uncrosslinked, or can be crosslinked (e.g., when the polymer has at least one cross-linking group) with itself or with the metal-containing (meth)acrylate).
  • the optical absorbance of the dielectric film of this disclosure at wavelength of 308 nm, 355 nm, 365 nm, or 405 nm is at least about 0.1 ⁇ m -1 (e.g., at least about 0.5 ⁇ m -1 , at least about 1 ⁇ m -1 , at least about 2 ⁇ m -1 , at least about 3 ⁇ m -1 , at least about 5 ⁇ m -1 , at least about 7 ⁇ m -1 , or at least about 9 ⁇ m -1 ).
  • this disclosure features a method of preparing a dry film structure.
  • the method includes:
  • the carrier substrate is a single or multiple layer film, which can include one or more polymers (e.g., polyethylene terephthalate).
  • the protective layer substrate is a single or multiple layer film, which can include one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers have been described in, e.g., U.S. Application Publication No. 2016/0313642 .
  • the dielectric film in the dry film structure has not yet been exposed to a source of radiation or heat to, e.g., form a crosslinked film.
  • the dielectric film of the dry film can be delaminated from carrier layer as a self-standing dielectric film.
  • a self-standing dielectric film is a film that can maintain its physical integrity without using any support layer such as a carrier layer.
  • the self-standing dielectric film can include (e.g., before crosslinking): a) at least one fully imidized polyimide polymer; b) at least one metal-containing (meth)acrylate (e.g., an uncrosslinked metal-containing (meth)acrylate); and c) at least one catalyst (e.g., a catalyst capable of inducing polymerization reaction).
  • the self-standing dielectric film can be exposed to a source of radiation or heat to form a crosslinked self-standing dielectric film.
  • the crosslinked self-standing dielectric film can include: a) at least one fully imidized polyimide polymer; and b) at least one crosslinked metal-containing (meth)acrylates.
  • the self-standing dielectric film (either crosslinked or uncrosslinked) can be laminated to a substrate (e.g., a semiconductor substrate) using a vacuum laminator at about 50°C to about 140°C after pre-laminating of the dielectric film with a plane compression method or a hot roll compression method.
  • the dielectric film of the dry film structure can be laminated to a substrate (e.g., a semiconductor substrate) using a vacuum laminator at a temperature of about 60°C to about 140°C after pre-laminating of the dielectric film of the dry film structure with a plane compression method or a hot roll compression method.
  • a substrate e.g., a semiconductor substrate
  • the hot roll lamination the dry film structure can be placed into a hot roll laminator, the optional protective layer can be peeled away from the dielectric film/carrier substrate, and the dielectric film can be brought into contact with and laminated to a substrate using rollers with heat and pressure to form an article containing the substrate, the dielectric film, and the carrier substrate.
  • the dielectric film can then be exposed to a source of radiation or heat (e.g., through the carrier substrate) to form a crosslinked film.
  • the carrier substrate can be removed before exposing the dielectric film to a source of radiation or heat.
  • a dielectric film is prepared from a dielectric film forming composition of this disclosure by a process containing the steps of:
  • Coating methods for preparation of the dielectric film include, but are not limited to, spin coating, spray coating, roll coating, rod coating, rotation coating, slit coating, compression coating, curtain coating, die coating, wire bar coating, knife coating and lamination of dry film.
  • Semiconductor substrates could have circular shape such as wafers or could be panels.
  • semiconductor substrates could be a silicon substrate, a copper substrate, an aluminum substrate, a silicon oxide substrate, a silicon nitride substrate, a glass substrate, an organic substrate, a copper cladded laminate or a dielectric material substrate.
  • the dielectric film of this disclosure can have a relatively low CTE.
  • the dielectric film of this disclosure can have a CTE measured at temperature range of 50 - 150°C of at most about 100 ppm/°C (e.g., at most about 95 ppm/°C, at most about 90 ppm/°C, at most about 85 ppm/°C, at most about 80 ppm/°C, at most about 75 ppm/°C, at most about 70 ppm/°C, at most about 65 ppm/°C, at most about 60 ppm/°C, at most about 55 ppm/°C, or at most about 50 ppm/°C) and at least about 15 ppm/°C (e.g., at least about 20 ppm/°C, at least about 30 ppm/°C, or at least 40 ppm/°C).
  • Film thickness of the dielectric film of this disclosure is not particularly limited.
  • the dielectric film has a film thickness of at least about 3 microns (e.g., at least about 4 microns, at least about 5 microns, at least about 7 microns, at least about 10 microns, at least about 15 microns, at least about 20 microns, or at least about 25 microns) and/or at most about 100 microns (e.g., at most about 80 microns, at most about 60 microns, at most about 50 microns, at most about 40 microns, or at most about 30 microns).
  • the dielectric film can have a relatively small film thickness (e.g., at most about 5 microns, at most about 4 microns, or at most about 3 microns).
  • the dielectric film then can be exposed to a source of radiation or to heat (e.g., to form a crosslinked film).
  • a source of radiation or to heat e.g., to form a crosslinked film.
  • radiation used for radiation exposure include electron beams, ultraviolet light and X-ray, with ultraviolet light being preferable.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an extra-high-pressure mercury lamp, or a halogen lamp can be employed as a radiation source.
  • the exposure dose is not particularly limited and one skilled in the art can easily determine the proper amount.
  • the exposure dose is at least about 100 mJ/cm 2 (e.g., at least about 200 mJ/cm 2 , or at least about 500 mJ/cm 2 ) and at most about 2,000 mJ/cm 2 (e.g., at most about 1,500 mJ/cm 2 or at most about 1,000 mJ/cm 2 ).
  • the heating temperature is at least about 70°C (e.g., at least about 100°C, at least about 130°C, or at least about 160°C) and/or at most about 250°C (e.g., at most about 220°C, at most about 200°C, or at most about 180°C).
  • the heating time is at least about 10 minutes (e.g., at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, or at least about 50 minutes) and/or at most about 5 hours (e.g., at most about 4 hours, at most about 3 hours, at most about 2 hours, or at most about 1 hour).
  • this disclosure features a process for depositing a metal layer (e.g., to create an embedded copper trace structure) that includes the step of:
  • Steps a) and b) can be the same as discussed earlier.
  • Patterned structures described in this disclosure can be obtained by a laser ablation process.
  • Direct laser ablation process with an excimer laser beam is generally a dry, one step material removal to form openings (or patterns) in the dielectric film.
  • the wavelength of the laser is 351 nm or less (e.g., 351 nm, 308 nm, 248 nm or 193 nm). In some embodiments, the wavelength of laser is 308 nm or less.
  • suitable laser ablation processes include, but are not limited to, the processes described in US patent numbers US7,598,167 , US6,667,551 , and US6,114,240 . Laser ablation processes using conventional dielectric films create large amounts of debris.
  • An important feature of this disclosure is that when the dielectric film prepared from the compositions of this disclosure is patterned by laser ablation process, little or no debris is formed, which results in less process complexity and lower cost.
  • One method of describing the level of debris is by using a scale of 1 to 5, in which1 represents the least amount of debris (no debris) and 5 represents the highest amount of debris produced by laser ablation process.
  • the debris generated by laser ablation process of the dielectric films prepared from the dielectric film forming compositions of this disclosure is at most 3 (e.g., at most 2 or at most 1).
  • Some embodiments of this disclosure describes a process to deposit a metal layer (e.g., an electrically conductive copper layer to create an embedded copper trace structure) on a semiconductor substrate.
  • a metal layer e.g., an electrically conductive copper layer to create an embedded copper trace structure
  • a seed layer conformal to the patterned dielectric film is first deposited on the patterned dielectric film (e.g., outside the openings in the film).
  • Seed layer can contain a barrier layer and a metal seeding layer (e.g., a copper seeding layer).
  • the barrier layer and metal seeding layer can be deposited on the patterned dielectric film (in or outside of the openings in the film) without the need of using a pretreatment process (e.g., by applying a chemical treatment, applying a plasma treatment, or using an external adhesive layer) to ensure good adhesion between the dielectric film and the seeding layer.
  • the barrier layer is prepared by using materials capable of preventing diffusion of an electrically conductive metal (e.g., copper) through the dielectric layer.
  • Suitable materials that can be used for the barrier layer include, but are not limited to, tantalum (Ta), titanium (Ti), tantalum nitride (TiN), tungsten nitride (WN), and Ta/TaN.
  • a suitable method of forming the barrier layer is sputtering (e.g., PVD or physical vapor deposition). Sputtering deposition has some advantages as a metal deposition technique because it can be used to deposit many conductive materials, at high deposition rates, with good uniformity and low cost of ownership. Conventional sputtering fill produces relatively poor results for deeper, narrower (high-aspect-ratio) features. The fill factor by sputtering deposition has been improved by collimating the sputtered flux. Typically, this is achieved by inserting between the target and substrate a collimator plate having an array of hexagonal cells.
  • a thin metal (e.g., an electrically conductive metal such as copper) seeding layer can be formed on top of the barrier layer in order to improve the deposition of the metal layer (e.g., a copper layer) formed in the succeeding step.
  • an electrically conductive metal such as copper
  • Next step in the process is depositing of an electrically conductive metal layer (e.g., a copper layer) on top of the metal seeding layer in the openings of the patterned dielectric film wherein the metal layer is sufficiently thick to fill the openings in the patterned dielectric film.
  • the metal layer to fill the openings in the patterned dielectric film can be deposited by plating (such as electroless or electrolytic plating), sputtering, plasma vapor deposition (PVD), and chemical vapor deposition (CVD).
  • Electrochemical deposition is generally a preferred method to apply copper since it is more economical than other deposition methods and can flawlessly fill copper into the interconnect features. Copper deposition methods generally should meet the stringent requirements of the semiconductor industry.
  • copper deposits should be uniform and capable of flawlessly filling the small interconnect features of the device, for example, with openings of 100 nm or smaller.
  • This technique has been described, e.g., in U.S. patent numbers US5,891,804 (Havemann et al. ), US6,399,486 (Tsai et al. ), US7,303,992 (Paneccasio et al. ).
  • the patterned dielectric film includes at least one element having a feature size (e.g., width) of at most about 10 microns (e.g., at most about 9 microns, at most about 8 microns, at most about 7 microns, at most about 6 microns, at most about 5 microns, at most about 4 microns, at most about 3 microns, at most about 2 microns, or at most about 1 micron).
  • a feature size e.g., width
  • the dielectric films prepared from the dielectric film forming composition described herein are capable of producing patterned with feature size of at most about 3 microns (e.g., at most 2 microns or at most 1 micron) by a laser ablation process.
  • the aspect ratio (ratio of height to width) of a feature (e.g., the smallest feature) of the patterned dielectric film of this disclosure is at least about 1/3 (e.g., at least about 1/2, at least about 1/1, at least about 2/1, at least about 3/1, at least about 4/1, or at least about 5/1).
  • the process of depositing an electrically conductive metal layer further includes removing overburden of the electrically conductive metal or removing the seed layer (e.g., the barrier layer and the metal seeding layer).
  • the overburden of the electrically conductive metal layer or the seed layer is minimized and can be removed by a relatively simple method, such as wet etching.
  • the overburden of the electrically conductive metal layer is at most about 3 microns (e.g., at most about 2.8 microns, at most about 2.6 microns, at most about 2.4 microns, at most about 2.2 microns, at most about 2.0 microns, or at most about 1.8 microns) and at least about 0.4 micron (e.g., at least about 0.6 micron, at least about 0.8 micron, at least about 1 micron, at least about 1.2 microns, at least about 1.4 microns or at least about 1.6 microns).
  • Examples of copper etchants for removing copper overburden include an aqueous solution containing cupric chloride and hydrochloric acid or an aqueous mixture of ferric nitrate and hydrochloric acid.
  • Examples of other suitable copper etchants include, but are not limited to, the copper etchants described in US patent numbers US4,784,785 , US3,361,674 , US3,816,306 , US5,524,780 , US5,650,249 , US5,431,776 , and US5,248,398 , and US application number US2017175274 .
  • the seed layer (e.g., the barrier layer and the metal seeding layer) can also be removed by wet etching.
  • suitable titanium etchants for removing a titanium barrier layer include, but are not limited to, hydrofluoric acid and a combination of nitric acid and hydrofluoric acid.
  • suitable titanium etchants include, but are not limited to, the titanium etchants described in US patent numbers US4,540,465 and US8,801,958 .
  • tantalum etchants for removing a tantalum barrier layer include, but are not limited to, aqueous solutions of sodium hydroxide/hydrogen peroxide and aqueous solutions of potassium hydroxide/hydrogen peroxide.
  • FIG. 1 is an illustrative scheme showing a conventional process for depositing a conductive metal (e.g., copper) on a patterned dielectric film.
  • a conventional dielectric film composition is deposited on a semiconductor substrate.
  • the dielectric film is patterned by using a laser ablation process.
  • the debris generated during the step 110 is removed (e.g., by chemical treatment using a cleaner or debris remover).
  • a pretreatment process to improve adhesion between a typical dielectric film and seed layer (e.g., including a barrier layer and a seeding layer) is shown in step 130.
  • a pretreatment process involving either a chemical treatment or a plasma treatment or applying an external adhesion promoter is necessary.
  • a desmear process of heating the dielectric film with potassium permanganate and sodium hydroxide solution is generally employed to improve adhesion of the dielectric film with the seed layer.
  • seed layer is deposited in step 140, followed by deposition of an electrically conductive metal in step 150.
  • Chemical mechanical polishing (CMP) is done to remove any overburden of the electrically conductive metal in step 160.
  • CMP chemical mechanical polishing
  • a post CMP cleaning is performed to obtain a semiconductor structure having embedded conductive metal traces.
  • FIG. 2 is an illustrative scheme showing an exemplary inventive process of this disclosure.
  • an inventive dielectric film of this disclosure can be formed by depositing a dielectric film forming composition described herein on a semiconductor substrate in step 200.
  • This coated dielectric film can be patterned by a laser ablation process in step 210, which generates little or no debris.
  • a seed layer e.g., including a barrier layer and a seeding layer
  • electrically conductive metal e.g., copper
  • the process can be completed by performing a wet etching process to remove any overburden of the electrically conductive metal or the seed layer to obtain a semiconductor structure having embedded conductive metal traces.
  • this disclosure features a three dimensional object containing at least one patterned film formed by a process described herein.
  • the three dimensional object can include patterned films in at least two stacks (e.g., at least three stacks). Examples of such objects include a semiconductor substrate, a flexible film for electronics, a wire isolation, a wire coating, a wire enamel, or an inked substrate.
  • this disclosure features semiconductor devices that include one or more of these three dimensional objects. Examples of such semiconductor devices include an integrated circuit, a light emitting diode, a solar cell, and a transistor.
  • Dielectric film forming compositions of Examples 1 - 6 and comparative Example 1 were prepared by mechanically stirring of a mixture of polymer (P-1), appropriate amount of methacryloxypropyl trimethoxysilane, NCI-831 (trade name, available from ADEKA corporation), titanium tetra(carboxyethyl acrylate) (MCA, 60 weight % in n-butanol), silica, cyclohexanone and crosslinkers. After being stirred mechanically for 24 hours, the solution was used without filtration.
  • the compositions of these Examples are shown in Table 2.
  • Crosslinker 1 is CN 992, (trade name available from Arkema - Sartomer), crosslinker 2 (CL-2) is tetraethylene glycol diacrylate, and crosslinker 3 (CL-3) is trimethylolpropane triacrylate
  • Each dielectric film forming composition was spin coated on a silicon wafer and baked at 95°C for 10 minutes using a hot plate to form a coating.
  • the film was then flood exposed with a broadband UV exposure tool (Carl Süss MA-56) at 500mJ/cm 2 and baked at 170°C for 2 hours to form a film with a thickness of about 6 to 9 microns.
  • the film was patterned by laser ablation process by using XeCl laser at a wave length of 308 nm at a frequency of 100 Hz.
  • the debris generated by the laser ablation process for each case is shown in Examples 7 -12 and Comparative Example 2 in the Table 3.
  • Example No Dielectric film forming composition Example Number Weight% of polyimide and MCA in total solid Debris Rating 1 - Best 5 - Worst Polyimide MCA Example 7 Example 1 24% 15% 1 Example 8 Example 2 19% 12% 1 Example 9 Example 3 23% 8% 2 Example 10 Example 4 27% 14% 2 Example 11 Example 5 37% 15% 2 Example 12 Example 6 56.39% 19% 3 Comparative Example 2 Comparative Example 1 65% N/A 5
  • compositions of Examples 1 to 6 (which all had a fully imidized polyimide polymer and an MCA) generated little or no debris (i.e., with a debris rating of 3 or less) after the laser ablation process.
  • composition of Comparative Example 1 (which is a conventional dielectric film forming composition without an MCA) generated a significant amount of debris (i.e., with a debris rating of 5) after the laser ablation process.
  • the amounts of polyimide polymer and MCA were calculated based on the percentages of these two compounds in total solid.
  • the weight of the total solid is defined as the entire weight of a dielectric film forming composition minus the entire weight of the solvent(s) of this composition.
  • Example 13 Laser Ablation and Deposition of a Barrier Layer
  • Barrier layer (titanium) was deposited at the top the patterned film using sputtering technique. The deposition was performed using Denton Vacuum Desktop unit at an electric current of 56 mA. A titanium barrier layer having a thickness of 26 nm was formed in 16 minutes.
  • the copper seeding layer was deposited at the top of the above barrier layer by using the same sputtering tool.
  • a copper seeding layer having a thickness of 420 nm was formed in 60 minutes at an electric current of 50 mA.
  • Electroplating was performed in a plating unit designed for wafers of different sizes.
  • a power source in the form of a rectifier (which converts alternating current electricity to regulated low-voltage DC current) provided the necessary current.
  • the work-piece (wafer) obtained above was cleaned with 10% H 2 SO 4 followed by deionized water rinse.
  • Electrodes, immersed in the electroplating bath (main ingredients: 3% Methanesulfonic acid and 5% CuSO 4 .5H 2 O in deionized water as electrolyte), were connected to the output of a DC current source.
  • the wafer to be electroplated acted as negatively charged cathode.
  • the positively charged anode completes the electric circuit.
  • the electroplating bath was maintained at 25°C while the electrolyte was re-circulated at a rate of 6 gallons per minute.
  • the cell was designed to have a baffle with proper inserts. Copper was deposited at the rate of one micron per minute when a current of 4.4 amperes and a voltage of 8.8 volts were maintained.
  • the copper overburden was 2 microns.
  • Copper etchant was prepared by first preparing a mixture of 90% deionized water and 10% cupric chloride, followed by adjusting the pH to 1 by addition of hydrochloric acid. The wafer obtained above was immersed in the copper etchant such that 2 microns copper overburden was removed at room temperature after 20 minutes. Titanium etchant was prepared by blending 98.994% deionized water, 1% hydrofluoric acid and 0.006% polyethyleneimine (MW of 200 Daltons). The wafer obtained above was immersed in the titanium etchant such that the barrier layer (26 nm) was removed at room temperature in one minute. A wafer having an embedded copper trace structure was obtained.
  • a debris removal composition consisting of 2.5 wt% tetramethyl ammonium hydroxide (TMAH), 7.5 wt% deionized water, 0.5 wt% hydroxylamine sulfate, 4.3 wt% monomethanol amine, 85 wt% tetrahydrofurfuryl alcohol, and 0.2 wt% 5-methyl-1H-benzotriazole was used.
  • TMAH tetramethyl ammonium hydroxide
  • This debris removal composition was heated to 60°C and the wafer was treated by immersing the wafer in the debris removal composition for 5 minutes. The wafer was washed with water and then dried. Debris was completely removed after this treatment.
  • Barrier layer (titanium) was deposited at the top the patterned film of Comparative Example 3 using sputtering technique. The deposition was performed using Denton Vacuum Desktop unit at an electric current of 56 mA. A titanium barrier layer having a thickness of 26 nm was formed in 16 minutes.
  • the copper seeding layer was deposited at the top of the above barrier layer by using the same sputtering tool.
  • a copper seeding layer having a thickness of 420 nm was formed in 60 minutes at an electric current of 50 mA.
  • Electroplating was performed in the same way that was described in Example 15, except for a longer time.
  • the copper overburden was 20 microns.
  • Copper overburden was removed by a CMP process. Copper bulk slurry was used on Mirra AMAT polisher with a slurry flow rate of 175 mL/min. The total time for the CMP process was 10 minutes. Upon completion of this polishing step, the wafer was cleaned in acidic cleaner, which removed organic residues and particles stuck to the surface of the wafer.
  • the titanium barrier layer was removed by a copper barrier slurry which was more mechanically driven than the bulk slurry, enabling efficient removal of this layer.
  • the wafer was cleaned in a second acidic cleaner, which removed organic residues and particles stuck to the surface of the wafer.
  • Example 17 Optical Absorbance Measurement of Dielectric Film Forming Composition of Example 1
  • the dielectric film forming composition of Example 1 was spin coated on top of a transparent 4" glass wafers at thickness of 3.0 um and soft baked at 95°C for 180 seconds.
  • the Absorbance of this self-standing dry film was measured by using a CARY 400 Conc. UV-Visible Spectrophotometer at a wavelength ranging from 300 to 405 nm.
  • Optical absorbance of this film was 0.383 ⁇ m -1 at 308 nm, 0.125 ⁇ m -1 at 355 nm, 0.127 ⁇ m -1 at 365 nm, and 0.058 ⁇ m -1 at 405 nm.
  • Dielectric film forming composition of Example 18 was prepared by using 339.00 g of polymer (P-1), 18.00 g of methacryloxypropyl trimethoxysilane, 10.80 g of OXE-01 (trade name, available from BASF SE), 114.00 g of titanium tetra(carboxyethyl acrylate) (60 weight % in n-butanol), 340.11 g of cyclohexanone, 126.00 g of tetraethylene glycol diacrylate available from Arkema - Sartomer and 252.0 g of urethane acrylate (CN 992, trade name available from Arkema - Sartomer). After being stirred mechanically for 24 hours, the composition was filtered by using a 0.2 micron filter.
  • Example 19 Dry film Example 1 (DF-1)
  • the filtered dielectric film forming composition of Example 18 was applied using a slot die coater from Fujifilm USA (Greenwood, SC) with line speed of 2 feet/minutes (60 cm per minutes) with 30 microns microbar clearance onto a polyethylene terephthalate (PET) film (Hostaphan 3915, manufactured by Mitsubishi Polyester Film, Inc.) having a width of 20.2 inches and thickness of 35 microns used as a carrier substrate and dried at 197°F to obtain a dielectric layer with a thickness of approximately 10.0 microns.
  • PET polyethylene terephthalate
  • a biaxially oriented polypropylene film having a width of 20.2 inches and a thickness of 20 microns was laid over by a roll compression to act as a protective layer.
  • Dielectric film forming composition of Example 20 was prepared by using 470.98 g of polymer (P-1), 15.00 g of methacryloxypropyl trimethoxysilane, 9.00 g of NCI-831 (trade name, available from ADEKA corporation), 175.00 g of titanium tetra(carboxyethyl acrylate) (60 weight % in n-butanol), 289.04 g of cyclohexanone, 141.00 g of tetraethylene glycol diacrylate available from Arkema - Sartomer, 750 g of 20% silica dispersed in cyclohexanone, and 150.00 g of urethane acrylate (CN 992, trade name available from Arkema - Sartomer). After being stirred mechanically for 24 hours, the solution was used without filtration.
  • P-1 polymer
  • methacryloxypropyl trimethoxysilane 9.00 g of NCI-831 (trade name, available from ADEKA
  • Example 21 Dry film Example 2 (DF-2)
  • the unfiltered dielectric film forming composition of Example 20 was applied using a slot die coater from Fujifilm USA (Greenwood, SC) with line speed of 2 feet/minutes (60 cm per minutes) with 30 microns microbar clearance onto a polyethylene terephthalate (PET) film (Hostaphan 3915, manufactured by Mitsubishi Polyester Film, Inc.) having a width of 20.2 inches and thickness of 35 microns used as a carrier substrate and dried at 197°F to obtain a dielectric layer with a thickness of approximately 10.0 microns.
  • PET polyethylene terephthalate
  • a biaxially oriented polypropylene film having a width of 20.2 inches and a thickness of 20 microns was laid over by a roll compression to act as a protective layer.
  • Formulation Example 22 is prepared by using 28.00 g of polymer (Poly-1), 46.88 g of cyclopentanone, 80.00 g of cyclohexanone, 0.84 g of N-(3-trimethoxysilylpropyl) pyrole, 1.40 g of 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (OXE-02, available from BASF), 6.20 g of hafnium tetracarboxyethyl acrylate, 11.00 g of titania with a medium size of 0.45 microns, 14 g of triethylene glycol dimethacrylate, 17.50 g of CN992 (available from Sartomer), 0.84 g of 0.05% solution of Polyfox 6320 in cyclopentanone, and 0.07 g of p-benzoquinone. After being stirred mechanically for 24 hours, the
  • Formulation Example 23 is prepared by using 26.00 g of polymer (Poly-1), 47.00 g of cyclopentanone, 75.00 g of cyclohexanone, 0.80 g of N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, 01.50 g of benzoyl peroxide, 7.50 g of zirconium butoxide tri(meth)acrylate, 17.0 g of tetraethylene glycol Diacrylate (SR-209, available from Sartomer), 14.00 g of pentaerythritol triacrylate, 0.72 g of 0.05% solution of Polyfox 6320 in cyclopentanone, and 0.05 g of p-benzoquinone. After being stirred mechanically for 30 hours, the formulation is used without filtration

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Claims (15)

  1. Composition de formation de film diélectrique, comprenant :
    a) au moins un polymère de polyimide totalement imidisé, l'au moins un polymère totalement imidisé étant imidisé à au moins 90 % ;
    b) au moins un (méth)acrylate contenant un métal, l'au moins un (méth)acrylate contenant un métal comprenant au moins un atome métallique et au moins un ligand (méth)acrylate ;
    c) au moins un catalyseur ; et
    d) au moins un solvant.
  2. Composition de la revendication 1, dans laquelle l'atome métallique de l'au moins un (méth)acrylate contenant un métal est choisi dans le groupe constitué par le titane, le zirconium, le hafnium et le germanium.
  3. Composition de la revendication 1, dans laquelle l'au moins un (méth)acrylate contenant un métal comprend le tétra(méth)acrylate de titane, le tétra(méth)acrylate de zirconium, le tétra(méth)acrylate de hafnium, le tri(méth)acrylate de butoxyde de titane, le di(méth)acrylate de dibutoxyde de titane, le (méth)acrylate de tributoxyde de titane, le tri(méth)acrylate de butoxyde de zirconium, le di(méth)acrylate de dibutoxyde de zirconium, le (méth)acrylate de tributoxyde de zirconium, le tri(méth)acrylate de butoxyde de hafnium, le di(méth)acrylate de dibutoxyde de hafnium, le (méth)acrylate de tributoxyde de hafnium, le tétra(carboxyéthyl(méth)acrylate) de titane, le tétra(carboxyéthyl(méth)acrylate) de zirconium, le tétra(carboxyéthyl(méth)acrylate) de hafnium, le tri(carboxyéthyl(méth)acrylate) de butoxyde de titane, le di(carboxyéthyl(méth)acrylate) de dibutoxyde de titane, le (carboxyéthyl(méth)acrylate) de tributoxyde de titane, le tri(carboxyéthyl(méth)acrylate) de butoxyde de zirconium, le di(carboxyéthyl(méth)acrylate) de dibutoxyde de zirconium, le (carboxyéthyl(méth)acrylate) de tributoxyde de zirconium, le tri(carboxyéthyl-(méth)acrylate) de butoxyde de hafnium, le di(carboxyéthyl(méth)acrylate) de dibutoxyde de hafnium, ou le (carboxyéthyl(méth)acrylate) de tributoxyde de hafnium, et/ou dans laquelle l'au moins un (méth)acrylate contenant un métal est présent dans une quantité allant d'environ 0,5 % en poids à environ 20 % en poids de la composition.
  4. Composition de la revendication 1, dans laquelle l'au moins un polymère de polyimide totalement imidisé est présent dans une quantité allant d'environ 3 % en poids à environ 40 % en poids de la composition, et/ou
    dans laquelle l'au moins un solvant est présent dans une quantité allant d'environ 35 % en poids à environ 98 % en poids de la composition.
  5. Composition de la revendication 1, dans laquelle l'au moins un catalyseur comprend un photoinitiateur ou un initiateur thermique, et/ou dans laquelle l'au moins un catalyseur est présent dans une quantité allant d'environ 0,25 % en poids à environ 4 % en poids de la composition.
  6. Composition de la revendication 1, comprenant en outre au moins un agent de réticulation, éventuellement dans laquelle l'agent de réticulation comprend au moins deux groupes alcényle ou alcynyle.
  7. Composition de la revendication 1, comprenant en outre au moins une charge, éventuellement dans laquelle l'au moins une charge comprend une particule inorganique choisie dans le groupe constitué par la silice, l'alumine, le dioxyde de titane, la zircone, l'oxyde de hafnium, CdSe, CdS, CdTe, CuO, l'oxyde de zinc, l'oxyde de lanthane, l'oxyde de niobium, l'oxyde de tungstène, l'oxyde de strontium, l'oxyde de calcium et de titane, le titanate de sodium, le sulfate de baryum, le titanate de baryum, le zirconate de baryum et le niobiate de potassium.
  8. Film diélectrique, comprenant :
    a) au moins un polymère de polyimide totalement imidisé, l'au moins un polymère totalement imidisé étant imidisé à au moins 90 % ;
    b) au moins un (méth)acrylate contenant un métal, l'au moins un (méth)acrylate contenant un métal comprenant au moins un atome métallique et au moins un ligand (méth)acrylate ; et
    c) au moins un catalyseur, le film diélectrique étant éventuellement un film diélectrique autoportant.
  9. Procédé de dépôt d'une couche de métal conducteur, comprenant :
    a) le dépôt de la composition de la revendication 1 sur un substrat pour former un film diélectrique ;
    b) l'exposition du film diélectrique à une source de rayonnement ou de chaleur ;
    c) le modelage du film diélectrique pour former un film diélectrique à motif ayant des ouvertures ;
    d) le dépôt d'une couche de germination sur le film diélectrique à motif ; et
    e) le dépôt d'une couche de métal conducteur dans au moins une ouverture dans le film diélectrique à motif.
  10. Procédé de la revendication 9, comprenant en outre le retrait d'un excès du métal conducteur ou le retrait de la couche de germination, éventuellement dans lequel l'excès a une épaisseur d'environ 2 µm maximum.
  11. Procédé de la revendication 9, dans lequel le retrait de l'excès du métal conducteur ou le retrait de la couche de germination est effectué par gravure humide, éventuellement dans lequel l'exposition du film diélectrique à une source de rayonnement ou de chaleur comprend le chauffage du film diélectrique à une température allant d'environ 70 °C à environ 250 °C, éventuellement dans lequel le modelage du film diélectrique est effectué par un procédé d'ablation laser, éventuellement dans lequel le film diélectrique à motif comprend au moins un élément ayant une taille caractéristique d'environ 3 µm maximum, éventuellement dans lequel la couche de métal conducteur comprend du cuivre, éventuellement dans lequel la couche de germination est déposée sans utiliser un procédé de retrait de débris ou un procédé de prétraitement, éventuellement dans lequel le procédé est dépourvu d'un procédé de planarisation mécanochimique ou d'un procédé de nettoyage post-planarisation mécanochimique destiné à traiter un excès de métal conducteur.
  12. Procédé de préparation d'une structure de film sec, comprenant :
    (A) le dépôt sur un substrat de support d'une composition de formation de film diélectrique de la revendication 1 pour former une composition déposée ;
    (B) le séchage de la composition déposée pour former un film diélectrique ; et
    (C) éventuellement, l'application d'une couche protectrice sur le film diélectrique.
  13. Procédé de dépôt d'une couche de métal conducteur, comprenant :
    a) la formation d'un film diélectrique photosensible avec la composition de la revendication 1 sur un substrat ;
    b) l'exposition du film diélectrique à une source de rayonnement ou de chaleur ;
    c) le modelage de film diélectrique pour former un film diélectrique à motif ayant des ouvertures ;
    d) le dépôt d'une couche de germination sur le film diélectrique à motif ; et
    e) le dépôt d'une couche de métal conducteur dans au moins une ouverture dans le film diélectrique à motif, le dépôt d'une couche de métal conducteur formant un excès de métal conducteur ayant une épaisseur d'environ 2 µm maximum.
  14. Procédé de la revendication 13, comprenant en outre le retrait de l'excès de métal conducteur ou le retrait de la couche de germination, éventuellement dans lequel le retrait de l'excès de métal conducteur ou le retrait de la couche de germination est effectué par gravure humide, éventuellement dans lequel l'exposition du film diélectrique à une source de rayonnement ou de chaleur comprend le chauffage du film diélectrique à une température allant d'environ 70 °C à environ 250 °C, éventuellement dans lequel le modelage du film diélectrique est effectué par un procédé d'ablation laser, éventuellement dans lequel le film diélectrique à motif comprend au moins un élément ayant une taille caractéristique d'environ 3 µm maximum, éventuellement dans lequel la couche de métal conducteur comprend du cuivre, éventuellement dans lequel la couche de germination est déposée sans utiliser un procédé de retrait de débris ou un procédé de prétraitement, éventuellement dans lequel le procédé est dépourvu d'un procédé de planarisation mécanochimique ou d'un procédé de nettoyage post-planarisation mécanochimique destiné à traiter tout excès de métal conducteur.
  15. Film diélectrique, comprenant :
    a) au moins un polymère de polyimide totalement imidisé, l'au moins un polymère totalement imidisé étant imidisé à au moins 90 % ; et
    b) au moins un (méth)acrylate contenant un métal réticulé, l'au moins un (méth)acrylate contenant un métal comprenant au moins un atome métallique et au moins un ligand (méth)acrylate, le film diélectrique étant éventuellement un film diélectrique autoportant.
EP18773066.8A 2017-09-11 2018-02-28 Composition formant un film diélecttrique Active EP3478777B1 (fr)

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US201762556723P 2017-09-11 2017-09-11
US201762581895P 2017-11-06 2017-11-06
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JP (2) JP7140686B2 (fr)
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PH (2) PH12018550157A1 (fr)
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TWI766959B (zh) 2022-06-11
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JP2020533418A (ja) 2020-11-19
CN109789644B (zh) 2023-01-31
CN109790405B (zh) 2022-07-15
JP7140686B2 (ja) 2022-09-21
KR102456361B1 (ko) 2022-10-19
EP3478777A1 (fr) 2019-05-08
EP3478777A4 (fr) 2019-05-08
TW201912717A (zh) 2019-04-01
EP3478482B1 (fr) 2020-12-16
US10875965B2 (en) 2020-12-29
EP3478482A4 (fr) 2019-07-17
JP7140687B2 (ja) 2022-09-21
KR20200053389A (ko) 2020-05-18
US10563014B2 (en) 2020-02-18
CN109790405A (zh) 2019-05-21
EP3478482A1 (fr) 2019-05-08
PH12018550157A1 (en) 2019-09-09
US20190077913A1 (en) 2019-03-14
WO2019050566A1 (fr) 2019-03-14
TW201912677A (zh) 2019-04-01
PH12018550158A1 (en) 2019-09-09
TWI776863B (zh) 2022-09-11
CN109789644A (zh) 2019-05-21
KR102494132B1 (ko) 2023-01-31
US20190081001A1 (en) 2019-03-14

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